Polyphosphate compositions containing tallow methyl tauride and 2-mercaptothiazoline



United States Patent POLYPHOSPHATE COMPOSITIONS CONTAINING TALLOW METHYL TAURIDE AND Z-MERCAP- TOTHIAZOLINE Edgar E. Ruif, Bergenfield, N. J., assignor to Lever Brothers Company, New York, N. Y., a corporation of Maine N Drawing. Application January 9, 1956 Serial No. 557,853

Claims. (Cl. 252-137) This invention relates to detergent compositions containing tarnish inhibitors and more particularly to spraydried tripolyphosphate compositions containing an alkali metal tallow methyl tauride and Z-mercaptothiazoline as synergistic tarnish inhibitors.

Tripolyphosphate compositions are now widely used for detergent and other purposes. Aqueous solutions of such compositions when at certain pH values tend to tarnish German silver (a nickel-zinc-copper alloy) to a variety of shades from yellow to bluish-black, espe cially if the solutions are at elevated temperatures and are allowed to remain in contact with the metal for several minutes. Since German silver is frequently used for household articles commonly washed in tripolyphosphate-built detergent compositions, it is evident that this is a serious problem.

In developing a spray-dried tripolyphosphate detergent composition containing an organic anionic non-soap detergent or an organic nonionic nonsoap detergent it was found that 2-mercapto-thiazoline was an effective tarnish inhibitor for such compositions. However, it was also found that when tripolyphosphate compositions contain from about 10% to about 20% of an.

alkali metal carbonate, that 2-mercaptothiazoline no longer was effective as a tarnish inhibitor. This is clearly shown by the six examples presented below in Table I wherein the amounts of the components in the tripolyphosphate detergent compositions are expressed in percent by weight of the total composition at the time of mixing the components together with the exception of the Z-mercaptothiazoline tarnish inhibitor, the percent thereof being based on the weight of the tripolyphosphate present in the compositions. In the following six examples Pluronic L-64 is an organic nonionic nonsoap detergent compound having the empirical formula HO-(C H O) (C I-I O);,(C H O) H prepared by condensing ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol where b is an integer selected from the group consisting of 26 to 30 and a plus 0 is an integer such that the molecule contains from 40% to 50% of ethylene oxide and Oronite Dispersant NIW is an organic nonionic nonsoap detergent which is a polypropylene alkyl phenol averaging tetradecyl in the alkyl radical condensed with ethylene oxide to an average of 9 ethylene oxide groups.

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TABLE I Example N o 1 2 3 4 5 6 5 Pluronic L-6 l 8. 75 8. 75 8. 75 8. 75 8. 75 8. 75

Oronite Dispersant NIW 1.25 1.25 1.25 1.25 1.25 1.25 Pentasodinm Tripolyphosphate- 35. 00 35. 00 35. 00 35.00 35. 00 35. 00 Sodium Oarboxymethyl H ydroxyl0 ethyl Cellulose--. 0.50 0. 50 0. 50 0. 50 0. 50 0.50 Water 10. 00 10. 00 10. 00 10. 00 10. 00 10. 00 Sodium Sulfate--- 44. 50 40. 75 37.00 33. 25 29. 50 24. 50 Sodium Carbonate 0.00 3. 75 7. 50 11. 25 15. 0O 20. 00

Total 100.00 100.00 100.00 100.00 100.00 100. L0

2-mercaptothiazoline (based on tripolyphosphate) 0. 06 0. 06 0. 06 0. 06 0. 06 0. 00 Tarmsh Grade N 0-- 1 2 3 5 5 5 The tarnishing action of each of the above tripolyphosphate compositions on German silver was tested by the following procedure. Five grams of the tripolyphosphate detergent composition was dissolved in somewhat less than one quart of water at a temperature under 170 F. More water was then added to give a total volume of one quart. 300 mls. of the solution was placed in a beaker, and the temperature adjusted to F.- F. A strip of German silver metal, six inches by one inch which has been cleaned with a metal polish and rinsed and dried, was partially immersed in the solution and allowed to remain for one-half hour at 160 F.-170 F. The metal strip was then removed and dried with a cloth. The strip was visually examined for tarnish and the tarnish graded as follows.

Grade No. Degree of Tarnish N o tarnish.

Interface stain only.

Barely noticeable tarnish.

Slight tarnish.

Moderate tarnish.

Considerable (heavy) tarnish.

Severe, as when inhibitor is absent.

This test procedure was employed throughout the remaining examples herein set forth.

From Example 1 above it can be readily seen that a tripolyphosphate detergent composition containing at least one organic nonsoap detergent and containing Z-mercaptothiazoline produces only interface stain upon German silver when the composition does not contain an alkali metal carbonate. As the amount of alkali metal carbonate is increased and the amount of alkali metal sulfate supplemental builder correspondingly decreased, it can be seen that the Z-mercaptothiazoline loses its effectiveness as a tarnish inhibitor and becomes ineffective when the alkali metal carbonate content is within the range from about 10% to about 20%. The compositions of Examples l-6 were prepared as mechanical mixes rather than as spray-dried products in order that the proportions of sodium carbonate would not be altered by possible decomposition upon spray drying. It will be appreciated, however, that the results noted above also apply to spray-dried products.

In accordance with the instant invention it was found that spray-dried tripolyphosphate detergent compositions containing at least one organic nonsoap detergent and from about 10% to about 20% of an alkali metal carbonate could be provided with greatly improved tarnishing properties upon German silver when such compositions contain Z-mercaptothiazoline and an alkali metal tallow methyl tauride as synergistic tarnish inhibitors. The spray-dried detergent compositions of the present invention which will inhibit the formation of tarnish upon German silver will therefore comprise by weight from about 20% to about 50% of an alkali metal tripo1yphosphate, from about to about 15% total of at least one organic nonsoap detergent other than an alkali metal tallow methyl tauride selected from the group consisting of organic anionic nonsoap detergents and organic nonionic nonsoap detergents, from about to about 20% of an alkali metal carbonate, about 10% of an alkali metal silicate, from about 0.03% to about 0.06% of 2-mercaptothiazoline based on the weight of tripolyphosphate, from about 1.4% to about 8.6% of an alkali metal tallow methyl tauride based on the weight of tripolyphosphate, and the balance water and supplemental builders. These components and percentages thereof are expressed at the time of mixing the components together and prior to spray drying.

Any water-soluble alkali metal tripclyphosphate may be employed, examples thereof being pentasodium tripolyphosphate and pentapotassium tripolyphosphate. From about 20% to about 50%, and preferably about 35%, by weight of the alkali metal tripolyphosphate is present in the detergent composition as the heavy duty component thereof.

From about 5% to about total, and preferably about 10% total, by weight of at least one organic nonsoap detergent other than an alkali metal tallow methyl tauride is employed in the composition. The organic nonsoap detergents may be either organic anionic nonsoap detergents or organic nonionic nonsoap detergents.

The organic anionic nonsoap detergents include, by way of example, the alkylaryl sulfonates, a class of anionic detergents Well known in the art under this name. One example thereof is the sulfonated phenyl polypropylene alkanes, characterized by the branched chain structure of polypropylene and a tertiary alkyl carbon at the benzene ring, and having the following general structure:

CHzRz where M is hydrogen, an alkali metal or an organic amine cation, and R and R are alkyl, of the type formula C H and at least one R is a polypropylene group, the whole alkyl group containing preferably 12 to 15 carbon atoms. These are known compounds, whose preparation and properties are set forth in U. S. Patent No. 2,477,383 to Lewis, issued July 26, 1949; they are available in commerce under the trade names Oronite, Ultrawet, and Neolene.

Nonionic detergents include, for example, alkyl oxyether and ester and thioether and ester detergents having the following general formula:

where R is a straight or branched chain saturated or unsaturated hydrocarbon group having from 8 to 18 carbon atoms or an aralkyl group having a straight or branched chain saturated or unsaturated hydrocarbon group of from 8 to 18 carbon atoms attached to the aryl nucleus, and attached to A through the aryl nucleus, A is selected from the group consisting of ethereal oxygen and sulfur, carboxylic ester and thiocarboxylic ester groups and x is a number from 8 to 20. R can, for example, be a straight or branched chain octyl, nonyl, decyl, lauryl, myristyl, cetyl or stearyl group, or an alkyl aryl group such as octylbenzene, nonylbenzene, decylbenzene, stearylbenzene, etc. When R is alkyl it will be evident that the detergent can be regarded as derived from an alcohol, mercaptan, oxy or thio fatty acid of high molecular weight, by condensation with ethylene oxide. Typical of this class of alkyl ether are the condensation products of oleyl or dodecyl alcohol or mercaptan with from 8 to 17 moles of ethylene oxide, such as Emulfor ON, Nonic 218, and Sterox SE and SK. Typical alkyl esters are G1226, Renex (polyoxyethylene ester of tall oil acids), Sterox CD and Neutronyx 330 and 331 (higher fatty acid esters of polyethylene glycol).

When R is aralkyl, the detergent can be derived from an alkyl phenol or thiophenol.

The ethoxynated alkyl phenols and thiophenols have the following general formula:

where R is a straight or branched chain saturated or unsaturated hydrocarbon group having at least 8 carbon atoms up to approximately 18 carbon atoms, A is oxygen or sulfur, and x is a number from 8 to 20. R can, for example, be a straight or branched chain octyl, nonyl, decyl, lauryl, cetyl, myristyl or stearyl group. Typical are the condensation products of octyl and nonyl phenol and thiophenol with from 8 to 17 moles of ethylene oxide, available commercially under the trade names NIW, Antarox A-400, Igepal CA and CO, Triton X-100, Neutronyx 600, and Tergitol NFX.

The alkali metal carbonate may be, by way of example, sodium carbonate or potassium carbonate, from about 10% to about 20%, and preferably 15%, by weight thereof be employed in the detergent composition.

The alkali metal silicates may be sodium or potassium silicate, for example, the amount thereof being about 10%.

As noted above, one of the synergistic tarnish inhibitors is Z-mercaptothiazoline. From about 0.03% to about 0.06% thereof based on the weight of tripolyphosphate is employed in the spray-dried detergent composition.

The other synergistic tarnish inhibitor is an alkali metal tallow methyl tauride, from about 1.4% to about 8.6% thereof based on the weight of tripolyphosphate being employed in the detergent composition. Tallow methyl tauride is characterized by the following structure: RCON(CH )CH CH SO M, where M is an alkali metal, e. g., ammonium, sodium, or potassium, and RCO represents the mixed acyl radicals of the fatty acids present in tallow, i. e., myristic acid, palmitic acid, stearic acid, and oleic acid. The tallow methyl tauride may be prepared, for example, by interacting tallow acid chloride containing an appropriate basic compound, such as sodium hydroxide, with N-methyl taurine.

The balance of the spray-dried detergent composition is made up of water and supplemental builders. Supplemental builders may include alkali metal and alkaline earth metal sulfates, chlorides, and borates, such as sodium tetraborate, sodium sulfate, calcium sulfate, calcium chloride, sodium chloride, and sodium borate. The builders should be water-soluble.

In addition to or instead of the above mentioned supplemental inorganic salts, organic material, such as starch, polyethylene glycol, polyvinyl alcohols and salts of carboxymethylcellulose and carboxymethyl hydroxyethyl cellulose and perfumes and dyes may be used in minor proportions as builders.

The tripolyphosphate detergent compositions may be prepared by the conventional method of blending the ingredients thereof in an aqueous solution or slurry and then drying the resulting mixture in a spray dryer at elevated temperatures. It was found that with drum-dried tripolyphosphate detergent compositions that the synergistic tarnish inhibitors were not necessary in order to prevent the formation of tarnish by such compositions upon German silver. Accordingly, drum-dried tripolyphosphate detergent compositions are excluded from this invention.

The invention will be further explained by the following discussion. Drum-dried tripolyphosphate detergent compositions do not need the presence of synergistic tarnish inhibitors, since the components of such compositions do not decompose upon drum drying. Accordingly, the of alkali metal silicate added to the mixture of the composition prior to drum drying remains present in the same amount in the drum-dried product and is suflicient by itself in this amount to inhibit the formation of tarnish upon German silver by the tripolyphosphate. This, however, is not true of spray-dried tripolyphosphate detergent compositions.

In the conventional spray drying of tripolyphosphate detergent compositions there is a decomposition of a portion of the alkali metal tripolyphosphate into such products as alkali metal pyrophosphate. For example, an aqueous slurry of the 35 %-tripolyphosphate detergent composition in Example 7 below mixed at 160 F. without the synergistic tarnish inhibitors upon spray drying at an air inlet temperature of 400-450 F. contained about 10% of tetrasodium pyrophosphate as determined by wet analysis. There is also a decomposition of the alkali metal silicate into silica floc by the acidic breakdown products of the alkali metal tripolyphosphate, thereby reducing the silicate content to about 6-8%. Accordingly, there is an insufiicient amount of silicate present in the spray-dried product to inhibit the formation of tarnish. Moreover, the presence of pyrophosphate in the spray-dried product resulting from the decomposition of tripolyphosphate increases the tarnishing efiect of the spray-dried product, since alkali metal silicate is much less effective as a tarnish inhibitor against pyrophosphates than against tripolyphosphates.

The 10% of alkali metal silicate would be effective as a tarnish inhibitor in tripolyphosphate detergent compositions containing from 10% to 20% of alkali metal carbonate if there were no decomposition of the tripolyphosphate and silicate upon spray drying. Since there is such decomposition, it is necessary in accordance with the invention to employ the synergistic tarnish inhibitors therein.

The compositions of the invention will be further illustrated in connection with the following examples. Spraydried tripolyphosphate detergent compositions were prepared having the following percentage compositions by weight at the time of mixing the components together and prior to spray drying. In Examples 7-10 the fluorescent dye was the disodium salt of 4,4'-bis|[4-phenylamino- 6-[bis (2 hydroxyethyl)]arnino-s-triazine-2-ylamino]|-2,2' stilbene disulfonic acid.

Example 7 PART A Percent Pluronic L-64 8.75 Oronite Dispersant NIW 1.25 Pentasodium tripolyphosphate 35 Sodium silicate 10 Sodium carbonate Sodium carboxymethyl hydroxyethyl cellulose 0.5 Water 10 Fluorescent dye 0.03 Sodium sulfate 19.45 Z-mercaptothiazoline 1 0.02

Total 100 2-mercaptothiazollne (based on tripolyphosphate), 0.06%.

PART B Pluronic L-64 8.75 Oronite Dispersant NIW 1.25 Pentasodium tripolyphosphate 35 Sodium silicate 10 Sodium carbonate 15 Sodium carboxymethyl hydroxyethyl cellulose-.. 0.5 Water 10 Fluorescent dye 0.03 Sodium sulfate 18.95 Z-mercaptothiazoline 1 0.02 Sodium tallow methyl tauride 2 0.50

Total 1 Z-mercaptothiazoline (based on tripolyphosphate), 0.06%. 1 igodium tallow methyl tauride (based on tripolyphosphate),

Example 8 PART A Percent Pluronic L-64 8.75 Oronite Dispersant NIW 1.25 Pentasodium tripolyphosphate 35 Sodium silicate 10 Sodium carbonate 15 Sodium carboxymethyl hydroxyethyl cellulose 0.5 Water 10 Fluorescent dye 0.03 Sodium sulfate 19.45 2-mercaptothiazoline 1 0.02

Total 100 2-mercaptothiazollne (based on tripolyphosphate), 0.06%.

PART B Pluronic L-64 8.75 Oronite Dispersant NIW 1.25 Pentasodium tripolyphosphate 35 Sodium silicate 10 Sodium carbonate 15 Sodium carboxymethyl hydroxyethyl cellulose 0.5 Water 10 Fluorescent dye 0.03 Sodium sulfate 16.435 Monastral Blue (copper phthalocyanine) 0.005 Monastral Green (copper halophthalocyanine) 0.01 Z-mercaptothiazoline 1 0.02. Sodium tallow methyl tauride 2 3.00

Total 100 2-mercaptothiazoline (based on tripolyphosphate), 0.06%. 8 5506mm tallow methsl tauride (based on tripolyphosphate),

2-mercaptothlazoline (based on tripolyphosphate), 0.06%.

PART B The compositions in Part A of each of Examples 7-10 Sodium dodecylbenzene lfo atg 10 contained an alkali metal tripo-lyphosphate, at least one Sodium silicate 10 organic anionic or nonionic nonsoap detergent other than Sodium carbonate 15 an alkali metal tallow methyl tauride, an alkali metal Sodium carboxymethyl hydroxyethyl cellulose 5 carbonate, an alkali metal silicate, supplemental builders Fluorescent dye 3 and one of the synergistic tarnish inhibitors, namely 2- Water mercaptothiazoline. In these compositions Z-mercapto- Sodium ulfate 1 ,45 thiazoline alone was ineffective as a tarnish inhibitor, gmercaptothiazolinel 0,02 since the compositions tarnished German silver to 21 Sodium tallow methyl d 3,0 10 degree of tarnish ranging from slight tarnish to moderate tarnish. The compositions in Part B of each of Ex- Total 10m amples 710 were as noted above with the exception l2 e a t thi z li (based on tripolyphosphate), 006%, that an alkali metal tallow methyl tauride was also dium tallow t y a id a on p yp p a l added thereto so that each of these compositions con- Example 10 tained the synergistic tarnish inhibitors, namely 2-mercaptothiazoline and an alkali metal tallow methyl tauride. PART A The compositions in Part B showed a noticeable improve- Percent ment over the corresponding compositions in Part A, Sodlum haTdeWd'taHOW alcohol sulfate 10 thereby demonstrating the remarkable effectiveness of Pentasodlwn mpolyphosphate 35 the synergistic tarnish inhibitors. sodPlm slhcate 10 Various modifications and changes may be made in the Sodium carbonate 15 compositions of the invention without departing from the Sodlum carboxymethyl hydroxyethyl Cellulose" spirit of the invention or sacrificing any of the advan- Fluorescent dye tages thereof. Accordingly, it will be understood that 10 the invention is to be limited only within the scope of Sodlum Sulfate 19-45 the appended claims. 2-mercaptoth1azol1ne 1 0.02 1 Claim;

1. A spray-dried detergent composition comprising Total 100-0 from about 20% to about 50% of an alkali metal 2-rnercaptothiazoline (based on tripolyphosphate), 0.06%. tripolyphosphate which in aqueous solution tarnishcs PART B German silver, from about 5% to about 15% total of at Sodium hardened ta11ow alcohol lf t 10 least one organic nonsoap detergent other than an alkali pentasodium tripolyphosphate metal tallow methyl tauride selected from the group sodium Silicate 10 consisting of organic anionic nonsoap detergents and Sodium carbonate 5 35 organic nonionic nonsoap detergents, from about 10% Sodium carboxymethyl hydroxyethyl cellulose" 5 to about 20% of an alkali metal carbonate, about 10% Fluorescent dye 003 of an alakli metal silicate, from about 0.03% to about Water 10 0.06% of Z-mercaptothiazoline based on the weight of Sodium lf t 16,45 tripolyphosphate, and from about 1.4% to about 8.6% zmercaptothiazolinei 0'02 of an alkali metal tallow methyl tauride based on the Sodium tallow methyl i z weight of the tripolyphosphate; the amounts of said thiazoline and tauride being sutficient to inhibit the Total 1000 tarnishing and the components of the composition being 2-n1e1'cnptothiazo1ine (based on tripolyphosphate), 0.06%. P by welght at the tune of mlxmg thereof and 2 Sodium tallow methyl tannde (based on tripolyphosphatc), 0 prior to spray drylng. 36% 2. A spray-dried detergent composition as set forth The conditions set forth in Table II below were in claim 1 wherein the amount of alkali metal tripolyemployed in the spray drying of the compositions in phosphate is about 35%. Examples 7-10. 3. A spray-dried detergent composition as set forth in TABLE II Example No 7A 7B 8A 8B 9A 9B 10A 10B Percent Water in Slurry 20 18 20 29 29 32.6 36.2 20 Slurry Temperature (F.) 185 185 185 185 185 185 185 135 Total Mixing Time (minutes) 30 30 30 30 3O 30 30 30 Mixing Time After Phosphate Addition (minutes) 10 10 10 10 10 10 10 10 Tower Air Inlet Temperature (*F.) 500-000 540 500-000 600-650 540 540 540 540 The tarnishing action of each of the spray-dried deter- 00 claim 1 wherein the alkali metal tripolyphosphate is gent compositions in Examples 7-10 upon German silver pentasodium tripolyphosphate. was tested in accordance with the above described test 4. A spray-dried detergent composition as set forth procedure Th f ll i lt were t d, in claim 1 containing about 10% total of at least one organic nonsoap detergent. Tamish 65 5. spray-dried detergent composition as set forth E a1np1eN0 Grade Degree ofTa -nish 1n cla1m 1 wherein the organic nonsoap detergents are 9. mixture of (1) a compound having the empirical formula HO-(C H O) (C H -O) (C H O) H prepared 3 g gg g f gg by condensing ethylene oxide with a hydrophobic base 4 M oderatct arnish. 10 formed by the condensation of propylene oxide with g gg propylene glycol where b is an integer selected from 1 Intel-r ce stainonly. the group consisting of 26 to 30 and a plus 0 is an 3 integer such that the molecule contains from 40% to tarnish. of ethylene oxide, and (2) a polypropylene alkyl 7 phenol averaging tetradecyl in the alkyl radical con- 9 densed with ethylene oxide to an average of 9 ethylene oxide groups.

6. A spray-dried detergent composition as set forth in claim 1 containing about 15% of an alkali metal carbonate.

7. A spray-dried detergent composition as set forth in claim 1 wherein the alkali metal carbonate is sodium carbonate.

8. A spray-dried detergent composition as set forth in claim 1 wherein the alkali metal tallow methyl tauride is sodium tallow methyl tauride.

9. A spray-dried detergent composition comprising from about 20% to about 50% f pentasodium tripolyphosphate which in aqueous solution tarnishes German silver; from about to about total of a mixture of (1) a compound having the empirical formula HO(C H O) (C H O) (C H O) H prepared by condensing ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol where b is an integer selected from the group consisting of 26 to 30 and a plus 0 is an integer such that the molecule contains from 40% to 50% of ethylene oxide and (2) a polypropylene alkyl phenol averaging tetradecyl in the alkyl radical condensed with ethylene oxide to an average of 9 ethylene oxide groups; from about 10% to about of sodium carbonate; about 10% of sodium silicate; from about 0.03% to about 0.06% of Z-mercaptothiazoline based on the weight of tripolyphosphate; and from about 1.4% to about 8.6% of sodium tallow methyl tauride based on the weight of tripolyphosphate; the amounts of said thiazoline and tauride being sufficient to inhibit the tarnishing and the components of the composition being expressed by weight at the time of mixing thereof and prior to spray drying.

10. A spray-dried detergent composition comprising about of pentasodium tripolyphosphate which in aqueous solution tarnishes German silver; about 10% total of a mixture of (l) a compound having the empirical formula HO-(C H O) tIC H O) (C H O) I-I prepared by condensing ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol Where b is an integer selected from the group consisting of 26 to 30 and a plus c is an integer such that the molecule contains from to of ethylene oxide, and (2) a polypropylene alkyl phenol averaging tetradecyl in the alkyl radical condensed with ethylene oxide to an average of 9 ethylene oxide groups; about 15% of sodium carbonate; about 10% sodium silicate; from about 0.03% to about 0.06% of Z-mercaptothiazoline based on the Weight of tripolyphosphate; and from about 1.4% to about 8.6% of sodium tallow methyl tauride based on the Weight of tripolyphosphate; the amounts of said thiazoline and tauride being sulficient to inhibit the tarnishing and the components of the composition being expressed by weight at the time of mixing thereof and prior to spray drying.

References Cited in the file of this patent UNITED STATES PATENTS 2,486,922 Strain Nov. 1, 1949 2,618,603 Schaeffer Nov. 18, 1952 2,733,215 Rufi? Jan. 31, 1956 2,758,092 Peck Aug. 7, 1956 FOREIGN PATENTS 156,852 Australia June 4, 1954 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No 2,870,092

January 20, 1959 Edgar E Ruff It is herebj certified that error appears in the-printed specification of the above numbered patent requiring correction and that the said Letters Patent should read as corrected belo Column '7, Example 9, Part 13, line 2, after "Sodium dodecylbenzene sulfonate 10" insert Pentasodium tripolyphosphate 35 column 10, line 33,. list of references cited, under "FOREIGN PATENTS" for Australia June 4, 1954 read Australia June 3,: 1954 (SEAL) Attest:

KARL H, AXLINE Attesting Officer Signed and sealed this 12th day of May 1959..

ROBERT C. WATSON Commissioner of Patents UNITED STATES PATENT DFFICE CERTIFICATE OF 'COREECTION Patent No. 2,870,092 January 20 1959 Edgar E Ruff It is hereby certified that error appears 1 the-printed specifi ti of the above numbered patent requiring correctic and that the said Letter Patent should read as corrected below. 1

Column '7, Example 9, Part B, line 2, after "Sodium dodecylbenzene sulfonate 1Q" insert Pentasodium tripolyphosp hate 35 column 10, line 33,. list of references cited, 1 "FOREIGN PATENTS" f 156,852 Australia June 43.954

read

156, 852 Australia June 3,954

( Signed and sealed this 12th day Of1y l959 Attest:

KARL H. AXLINE ROBERT C. WATSON Attesting ()fli Commissioner of Patents UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 2 ,8'70 ,092 January 20, 1959 Edgar E. Ruff It is hereby certified that error appears in the-printed specification of the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column '7, Example 9, Part B, line 2, after "Sodium dodecylbenzene sulfonate 10" insert Pentasodium tripolyphosphate --'----n,--=- 35 column 10, line 33, list of references cited, under "FOREIGN PATENTS" for 56,852 Australia June 4, 1954 read I 156, 852 Australia June 3 1954 Signed and sealed this 12th day of May 1959 Attest: KARL H. AXLINE ROBERT C. WATSON Attesting Officer Commissioner of Patents 

1. A SPRAY-DRIED DETERGENT COMPOSITION COMPRISING FROM ABOUT 20% TO ABOUT 50% OF AN ALKALI METAL TRIPOLYPHOSPHATE WHICH IN AQUEOUS SOLUTION TARNISHES GERMAN SILVER, FROM ABOUT 5% TO ABOUT 15% TOTAL OF AT LEAST ONE ORGANIC NONSOAP DETERGENT OTHER THAN AN ALKALI METAL TALLOW METHYL TAURIDE SELECTED FROM THE GROUP CONSISTING OF ORGANIC ANIONIC NONSOAP DETERGENTS AND ORGANIC NONIONIC NONSOAP DETERGENTS FROM ABOUT 10% TO ABOUT 20% OF AN ALKALI METAL CARBONATE, ABOUT 10% OF AN ALKALI METAL SILICATE, FROM ABOUT 0.03% TO ABOUT 0.06% OF 2-MERCAPTOTHIAZOLINE BASED ON THE WEIGHT OF TRIPOLYPHOSPHATE, AND FROM ABOUT 1.4% TO ABOUT 8.6% OF AN ALKALI METAL TALLOW METHYL TAURIDE BASED ON THE WEIGHT OF THE TRIPOLYPHOSPHATE; THE AMOUNTS OF SAID THIAZOLINE AND TAURIDE BEING SUFFICIENT TO INHIBIT THE TARNISHING AND THE COMPONENTS OF THE COMPOSITION BEING EXPRESSED BY WEIGHT AT THE TIME OF MIXING THEREOF AND PRIOR TO SPRAY DRYING. 